A kind of barrier film for lithium rechargeable battery and the battery containing this barrier film
Technical field
The utility model relates to technical field of lithium ion secondary, particularly relates to a kind of barrier film for lithium rechargeable battery and the battery containing this barrier film.
Background technology
Lithium rechargeable battery is applied and consumption electronic product widely, and as mobile phone, notebook computer, panel computer, bluetooth earphone, MP3, the fields such as digital camera are widely used.Increasingly serious along with environmental pollution and problem of energy crisis, lithium rechargeable battery is also more and more universal in the use in the field such as electrokinetic cell and stationary electric power plant.
Along with improving constantly of energy density, the use of the negative material of high gram volume causes the expansion in its charge and discharge process serious, causes battery torsional deformation.In order to address this problem, the coating of surface-coated cohesive polymers of the inherent barrier film of industry or the mixed coating of inorganic particulate and cohesive polymers.As SDI patent CN1302575C, ATL patent CN102569701A, the patent CN101326658A of CN102610773A, CN103441230A and LG.This cohesive polymers can be swelling in electrolyte, in certain temperature, is bonded together in pressure and time with positive/negative plate, positive/negative plate and barrier film adhere to as a whole after can suppress the expansion of negative pole, the distortion of prevention battery.Under certain temperature and pressure can plane drawout after but cohesive polymers is swelling, for winding type battery, cohesive polymers coating can be assembled outside extruding and finally be caused Width can become large to two ends, exceed restriction width.
Utility model content
First object of the present utility model is: for the deficiencies in the prior art, and a kind of barrier film for lithium rechargeable battery is provided, efficiently solve the expansion of battery in charge and discharge process serious, cause the problem of battery torsional deformation, with for winding type battery, cohesive polymers coating can be assembled outside extruding and finally be caused Width can become large to two ends, and causes exceeding the phenomenon limiting width.
For achieving the above object, the utility model adopts following technical scheme:
A kind of barrier film for lithium rechargeable battery, comprise barrier film body and be coated on the functional coating of described barrier film body, described functional coating is polymeric layer, or be the mixed layer of inorganic particulate and polymer, described barrier film body has uncoated region, and described functional coating compartment of terrain is coated on described barrier film body.
Relative to prior art, the utility model beneficial effect is: the mixed coating by functional coating of the present utility model being cohesive polymers or inorganic particulate and cohesive polymers, functional coating is coated on the one or both sides of barrier film body, functional coating can bond well with pole piece, suppress cell deformation, cohesive polymers is sprawled in electrolyte swelling after heat pressing face and is assembled extruding to two ends simultaneously, the size of Width can not be increased, efficiently solve the expansion of battery in charge and discharge process serious, cause the problem of battery torsional deformation, with for winding type battery, cohesive polymers coating can be assembled outside extruding and finally be caused Width can become large to two ends, and cause exceeding the phenomenon limiting width.
Improve as one of the present utility model, described functional coating is coated on the one or both sides of described barrier film body with gap.In order to the winder formed when positive pole and negative pole reel more provides deformation space, suppress battery deformation to reach, the effect of protection battery performance.
Improve as one of the present utility model, described polymeric layer is polyvinylidene fluoride layer, polypropylene nitrile layer, polyoxyethylene layer or polymethacrylates layer.Kynoar (PVDF), polyacrylonitrile (PAN), polyoxyethylene (PEO) and polymethacrylates (PMMA) in the electrolytic solution can be swelling, thus with positive/negative plate, there is good adhesive property, the described functional coating utilizing above material to make can bond well with pole piece, suppress cell deformation, cohesive polymers is sprawled in electrolyte swelling after heat pressing face and is assembled extruding to two ends simultaneously.
Improve as one of the present utility model, described mixed layer is made up of at least one in Kynoar, polyacrylonitrile, polyoxyethylene and polymethacrylates and inorganic particulate, described inorganic particulate be in calcium oxide, zinc oxide, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, alundum (Al2O3), boehmite, calcium carbonate and barium titanate any one or multiple, described inorganic particulate has excellent thermal stability, the heat resistance of barrier film can be improved, improve the security performance of battery.
Improve as one of the present utility model, the area in described uncoated region and the area ratio value of described functional coating are 0.05 ~ 1, and preferably, the area in described uncoated region and the area ratio value of described functional coating are 0.1 ~ 0.5.The area ratio value of the area and described functional coating that control described uncoated region can be 0.05 ~ 1, to make the area in described uncoated region when positive pole and negative pole reel, winder obtains sufficient space, simultaneously described functional coating also can reach the good effect that to bond with pole piece, and flattening face at cohesive polymers in the swelling after heat of electrolyte sprawls to two ends gathering extruding, winding uncoated region, two ends gives over to cohesive polymers accumulation regions, thus suppress battery deformation, suppress cell widths to increase.Wherein, the area in described uncoated region and the area ratio value of described functional coating are 0.1 ~ 0.5, best results.
Improve as one of the present utility model, the thickness of described functional coating is 0.5 ~ 10 μm, and preferably, the thickness of described functional coating is 2 ~ 7 μm.When the thickness of functional coating is less than 0.5 μm, then because it is excessively thin, affect the caking property of itself and both positive and negative polarity, and can not play better and pole piece cementation; When the thickness of functional coating is greater than 10 μm, blocked up meeting makes the penalty of battery, is preferably 2 ~ 7 μm.
Second object of the present utility model is to provide a kind of lithium ion battery, comprise positive pole, negative pole, be interval in barrier film between positive pole and negative pole, and electrolyte, described barrier film is with the above-mentioned barrier film for lithium rechargeable battery, after described positive pole, described negative pole and described barrier film reel, described uncoated region is positioned at the bending part of the rear battery core of winding.
Relative to prior art, the beneficial effect of lithium ion battery of the present utility model is: the utility model contains the above-described barrier film for lithium rechargeable battery, making its cohesive polymers flatten face in the swelling after heat of electrolyte sprawls to two ends gathering extruding, the size of Width can not be increased, efficiently solve the expansion of battery in charge and discharge process serious, cause the problem of battery torsional deformation, with for winding type battery, cohesive polymers coating can be assembled outside extruding and finally be caused Width can become large to two ends, and cause exceeding the phenomenon limiting width.
Accompanying drawing explanation
Fig. 1 is the cutaway view of the utility model lithium rechargeable battery barrier film.
Fig. 2 is the structural representation of the utility model lithium rechargeable battery barrier film.
Fig. 3 is the structural representation of the utility model lithium rechargeable battery barrier film in battery winding.
Wherein: A1-barrier film body, A2-functional coating, the uncoated region of A3-, S1-binding part, S2-winder.
Embodiment
Below in conjunction with embodiment and Figure of description, the utility model is described in further detail, but execution mode of the present utility model is not limited thereto.As shown in Fig. 1 ~ 3.
embodiment 1
The preparation of barrier film:
By silicon dioxide (SiO
2) ceramic particle fully mixes in the solution with Kynoar (PVDF), obtains slurry.Then adopt the mode of printing coating to be coated in ceramic material gap on a face of barrier film body A1, form functional coating A2 and uncoated region A3, dry, obtain the barrier film that functional coating A2 at the thickness of barrier film body A1 is 2 μm.
The preparation of positive plate:
By cobalt acid lithium (LiCoO
2), conductive carbon (Super-P) and Kynoar (PVDF) according to 95: 2: 3 mass ratio mixing in a solvent, stir, obtain anode sizing agent.Slurry is coated on the aluminium foil of 9 μm, dry, cold pressing, obtain the pole piece that compacted density is 1.6g/cm3, then through cut-parts, soldering polar ear, obtain positive plate.
The preparation of negative plate:
By native graphite, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) according to 95: 2: 3 mass ratio mixing in a solvent, stir, obtain cathode size.Slurry is coated on the Copper Foil of 9 μm, dry, cold pressing, obtain the pole piece that compacted density is 1.7g/cm3, then through cut-parts, soldering polar ear, obtain negative plate.
The preparation of lithium ion battery:
The positive plate obtained, negative plate and barrier film are wound into battery core in order, with aluminium plastic membrane by battery core closedtop and side seal, leave liquid injection port.Then from liquid injection port perfusion electrolyte, the composition of electrolyte is vinyl carbonate (EC), propylene carbonate (PC), divinyl carbonic ester (DEC), and the ratio of three is 3: 3: 4, encapsulation.Then make to form cementation between electrode and barrier film by the mode of hot pressing, then through changing into, the operation such as capacity obtains lithium ion battery.
embodiment 2
The preparation of barrier film:
By titanium dioxide (TiO
2) fully mix with polymethacrylates (PMMA) solution, obtain slurry.Then adopt the mode of printing coating to be coated in ceramic material gap on a face of barrier film body A1, form functional coating A2 and uncoated region A3, dry, obtain the barrier film that functional coating A2 at the thickness of barrier film body A1 is 4 μm.
The preparation of positive plate:
By cobalt acid lithium (LiCoO
2), conductive carbon (Super-P) and Kynoar (PVDF) according to 95: 2: 3 mass ratio mixing in a solvent, stir, obtain anode sizing agent.Slurry is coated on the aluminium foil of 9 μm, dry, cold pressing, obtain the pole piece that compacted density is 1.6g/cm3, then through cut-parts, soldering polar ear, obtain positive plate.
The preparation of negative plate:
By native graphite, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) according to 95: 2: 3 mass ratio mixing in a solvent, stir, obtain cathode size.Slurry is coated on the Copper Foil of 9 μm, dry, cold pressing, obtain the pole piece that compacted density is 1.7g/cm3, then through cut-parts, soldering polar ear, obtain negative plate.
The preparation of lithium ion battery:
The positive plate obtained, negative plate and barrier film are wound into battery core in order, with aluminium plastic membrane by battery core closedtop and side seal, leave liquid injection port.Then from liquid injection port perfusion electrolyte, the composition of electrolyte is vinyl carbonate (EC), propylene carbonate (PC), divinyl carbonic ester (DEC), and the ratio of three is 3: 3: 4, encapsulation.Then make to form cementation between electrode and barrier film by the mode of hot pressing, then through changing into, the operation such as capacity obtains lithium ion battery.
embodiment 3
The preparation of barrier film:
Kynoar (PVDF) is fully mixed in CMC solution, obtains slurry.Then the mode of printing coating is adopted to be coated in slurry gap on two faces of barrier film body A1, form functional coating A2 and uncoated region A3, drying, obtains the barrier film that functional coating A2 is 3 μm (double thickness is 6um) at the thickness of barrier film body A1 one side.
The preparation of positive plate:
Cobalt acid lithium (LiCoO2), conductive carbon (Super-P) and Kynoar (PVDF) are mixed in a solvent according to the mass ratio of 95: 2: 3, stirs, obtain anode sizing agent.Slurry is coated on the aluminium foil of 9 μm, dry, cold pressing, obtain the pole piece that compacted density is 1.6g/cm3, then through cut-parts, soldering polar ear, obtain positive plate.
The preparation of negative plate:
By native graphite, conductive carbon (Super-P) and sodium carboxymethylcellulose (CMC) according to 95: 2: 3 mass ratio mixing in a solvent, stir, obtain cathode size.Slurry is coated on the Copper Foil of 9 μm, dry, cold pressing, obtain the pole piece that compacted density is 1.7g/cm3, then through cut-parts, soldering polar ear, obtain negative plate.
The preparation of lithium ion battery:
The positive plate obtained, negative plate and barrier film are wound into battery core in order, with aluminium plastic membrane by battery core closedtop and side seal, leave liquid injection port.Then from liquid injection port perfusion electrolyte, the composition of electrolyte is vinyl carbonate (EC), propylene carbonate (PC), divinyl carbonic ester (DEC), and the ratio of three is 3: 3: 4, encapsulation.Then make to form cementation between electrode and barrier film by the mode of hot pressing, then through changing into, the operation such as capacity obtains lithium ion battery.
A kind of barrier film for lithium rechargeable battery, comprise barrier film body A1 and be coated on the functional coating A2 of barrier film body A1, functional coating A2 is polymeric layer, or be the mixed layer of inorganic particulate and polymer, barrier film body A1 has uncoated region A3, functional coating A2 compartment of terrain is coated on barrier film body A1, and wherein, the region at functional coating A2 interval is exactly uncoated region A3.
By the mixed coating that functional coating A2 of the present utility model is cohesive polymers or inorganic particulate and cohesive polymers, functional coating A2 is coated on the one or both sides of barrier film body A1, functional coating A2 can bond well with pole piece, suppress cell deformation, cohesive polymers is sprawled in electrolyte swelling after heat pressing face and is assembled extruding to two ends simultaneously, the size of Width can not be increased, efficiently solve the expansion of battery in charge and discharge process serious, cause the problem of battery torsional deformation, with for winding type battery, cohesive polymers coating can be assembled outside extruding and finally be caused Width can become large to two ends, and cause exceeding the phenomenon limiting width.
Functional coating A2 compartment of terrain is coated on the one side of barrier film body A1.Be coated on barrier film body A1 by functional coating A2 compartment of terrain, for uncoated region A3 provides space, to ensure that uncoated region A3 has enough spaces, guarantee that uncoated region A3 is positioned at the two ends of battery core after the coiling, arrive the object suppressing cell deformation.
Functional coating A2 is coated on the two sides of barrier film body A1 with gap, is in order to more for the winder S2 formed when positive pole and negative pole winding provides deformation space, suppresses battery deformation, the effect of protection battery performance to reach.
Polymeric layer is polyvinylidene fluoride layer, polypropylene nitrile layer, polyoxyethylene layer or polymethacrylates layer.Kynoar (PVDF), polyacrylonitrile (PAN), polyoxyethylene (PEO) and polymethacrylates (PMMA) in the electrolytic solution can be swelling, thus with positive/negative plate, there is good adhesive property, the functional coating A2 utilizing above material to make can bond well with pole piece, suppress cell deformation, cohesive polymers is sprawled in electrolyte swelling after heat pressing face and is assembled extruding to two ends simultaneously.
Mixed layer is Kynoar, polyacrylonitrile, at least one in polyoxyethylene and polymethacrylates with form with inorganic particulate, described inorganic particulate be in calcium oxide, zinc oxide, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, alundum (Al2O3), boehmite, calcium carbonate and barium titanate any one or multiple.Described inorganic particulate has excellent thermal stability, can improve the heat resistance of barrier film, improves the security performance of battery.
The area of uncoated region A3 and the area ratio value of functional coating A2 are 0.05 ~ 1, and preferably, the area of uncoated region A3 and the area ratio value of functional coating A2 are 0.1 ~ 0.5.
The area ratio value of the area and functional coating A2 that control uncoated region A3 can be 0.05 ~ 1; to make the area of uncoated region A3 when positive pole and negative pole reel; winder S2 obtains sufficient space; simultaneously functional coating A2 also can reach the good effect that to bond with pole piece; and flattening face at cohesive polymers in the swelling after heat of electrolyte sprawls to two ends gathering extruding; suppress battery deformation, the effect of protection battery performance.Wherein, the area of uncoated region A3 and the area ratio value of functional coating A2 are 0.1 ~ 0.5, best results.
The thickness of functional coating A2 is 0.5 ~ 10 μm, and preferably, the thickness of functional coating A2 is 2 ~ 7 μm.When the thickness of functional coating A2 is less than 0.5 μm, then because it is excessively thin, can not play better and pole piece cementation; When the thickness of functional coating A2 is greater than 10 μm, blocked up meeting makes the penalty of battery, is preferably 2 ~ 7 μm.
A kind of lithium ion battery, comprise positive pole, negative pole, be interval in barrier film between positive pole and negative pole, and electrolyte, barrier film is the barrier film for lithium rechargeable battery of above any one, after positive pole, negative pole and barrier film reel, uncoated region A3 is positioned at the bending part of the rear battery core of winding.
The announcement of book and instruction according to the above description, the utility model those skilled in the art can also change above-mentioned execution mode and revise.Therefore, the utility model is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present utility model, replacement or modification all belong to protection range of the present utility model.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the utility model.